Control of catalyst hydration



June 1954 s. R. BETHEA 2,681,374

CONTROL OF CATALYST HYDRATION Filed April 14, 1951 WA TER AN)ALYZER I8 I5 II war OLEFINIC FEED WATER PACKIN6 WATER SEPA RA TOR MAKEUP ACID L 26 WATER BLEED 36 7% '/ACID SEPARATOR USED ACID I INVENTOR. gnfifiiifiew ing hydrocarbon feed water and the second molecule are polymerized.

y are the mono-olefins having 3 Patented June 15, 1954 2,681,374 CONTROL OF CATALYST HYDRATION Sam R. Bethea, Baytown,

assignments, to Stan Company, Elizabeth,

Delaware Tex., assignor, by mesne dard Oil Development N. J., a corporation of Application April 14, 1951, Serial No. 221,050

6 Claims.

1 The present invention is directed to the poly merization of olefins. More particularly; the invention is directed to polymerization of olefins employing a phosphoric acid catalyst.

The invention may be described as involving a method for maintaining the strength of a liquid phosphoric acid catalyst in a conversion operation in which a catalyst contacts a water-containin a vaporized condition at an elevated temperature in a reaction zone and a v product and liquid catalyst are withdrawn. The

invention includes the steps of withdrawing from the reaction zone first and second streams which are separately cooled. The first stream is a stream of vaporous hydrocarbons containing stream is a stream of hydrocarbon and acid catalyst. The cooled first and second streams are separated, respectively, into a first hydrocarbon phase and a water phase and into a second hydrocarbon phase and an acid phase. The water phase is discarded and the first and second hydrocarbon phases may be combined. The acid phase is recycled to the contacting step and has a strength substantially the same as the acid catalyst.

The invention is particularly applicable to a catalytic polymerization process in which monoolefins having from 3 to 6 carbon atoms in the The mono-olefins forming the feed stock of the include propylene, the butylenes, pentylenes and the hexylenes. Particularly desirable feed stocks and 4 carbon atoms in the molecule and including propylene and 1- and 2-butylene, and isobutylene.

The phosphoric acid employed in the practice of the present invention may have a strength in the range from about 75% to 115% by weight of H3PO4. A preferred acid strength is in the range from 100% to 110% H3PO'4. ployed in the polymerization operation in accordance with the present invention may range from 280 to about 450 F., the preferred range being between 300 and 400 F. Quite satisfactory results are obtained when polymerizing propylene at 360 F.

The two streams are separately cooled to a temperature in the range from 80 to 200 F. Cooling water ordinarily available in the refinery will allow the obtaining of such temperature.

The temperature to which the vaporous stream and the stream containing hydrocarbon and catalyst are cooled will ordinarily be sufiiciently low to condense any condensible hydrocarbons therei in which may be dissolved in the higher boiling present invention Temperatures em- Lil retained in the system,

hydrocarbons under the pressure employed in the system. Pressures employed in the practice of the present invention may range from about 300 to about 1000 lbs/sq. in. gauge or higher. The pressures may vary somewhat but are sufiiciently low to maintain the olefinic feed in a vaporous condition at the polymerization temperatures mentioned before.

The m0no-olefins and the liquid phosphoric acid catalyst are contacted in a reaction zone. The reaction zone is packedwith an inert, substantially non-adsorbent packing material over which the liquid phosphoric acid is distributed as a film to insure good contact with the vaporized olefin. Examples of the type of packing material suitable in the practice of the present invention are given in U. 8. Patent 2,136,785, issued to Davis on November 15, 1938. Besides the type of packing mentioned by Davis, supra, it is contemplated that the reaction vessel in accordance with the present invention may be filled or packed with other inert distributing means, such as carbon Raschig rings, or other well known carbon packing material which may be in the form of Berl a saddles and the like. Suitable packing materials are described in U. S. Patent 2,135,793 to Brooke phoric acid catalyst are introduced into the top The liquid catalyst flows down over the packing and out the bottom into a separator from which it is pumped back to the reactor inlet. Any hydrocarbon phase that may be conof the reactor.

densed in the reactor near the reactor outlet also gravitates to the bottom of the reactor.

As described, the vaporous stream is separately cooled to a temperature suiiiciently low to cause substantial condensation of the hydrocarbon and the water contained therein. The stream of hydrocarbon and catalyst are also separately cooled to allow substantial condensation of the hydrocarbon. By virtue of cooling the vaporous stream, the water contained therein is condensed and may be separated as a water phase. The only other water lost from the system will be that dissolved in the liquid hydrocarbon phase. Thus, by properly proportioning the vaporous stream and the stream of hydrocarbon and catalyst, it is possible to control exactly the amount of water and, consequently, the concentration of the acid catalyst.

The invention will now be described in more detail by reference to the drawing. in which the :bonaceous material.

which connects into line H and which is controlled by valve H3. The water-containing hydrocarbon feed passes into a water analyzer'lll which may be a suitable instrument for measuring water, such as a Fox. oro Dynalogue, whereby the water content of the hydrocarbon feed is measured continuously. The wet olefinic feed is introduced into the system in a vaporized condition and its temperature may be suitably adjusted to a temperature in the range between 280 and 400 F., suitable for polymerization in a manner tobe described. The olefinicfeed leaves analyzer is byline i5 and discharges thereby 'into a-reaction zone it containing a packedsection I! which maybe a suitable body .of inert packing material, such as that described before.

Phosphoric acid catalystis introduced into reaction zone It by line 'idfrom a source which will be described further and flows-concurrently with the vaporized olefinic reed over the packing ll, allowing intimate contact therewith and causing polymerization of the propylene contained therein. It is understood, of course, that the temperatures in reaction zone it are within the range given and that reaction zone it may be provided with heat control means to maintain a this temperature. Likewise, pressures are suitably adjusted on the system to maintain a vapor phase.

The reactionzone I6 is provided with a bafiie member 18a to allow'withdrawal of a vaporcus stream by line I9. Reaction zone i6 is also provided with -line 28 toallow withdrawal of a secondstream thereby. The vaporous stream withdrawn .by .line 19 is discharged thereby into a .cooler 2| which is provided with a cooling coil m) 22. The cooled stream then discharges by line 23 into a water separation zone 2A which is of sufficient capacity to allow a residence time .for separation of a water phase which is generally indicated by the shadedportion This water phase may be discharged from the system by line 26 while the hydrocarbons formingan upper layer in separator '24 are withdrawn by lineil.

Line i9 .is provided with a control valve 28 which is connected bysuitable connection means 29 to water analyzer i4. .ValveZB may be of the pneumatic type and may betcontrolled responsive to electrical signals from water analyzer M through control means 2 9.

,A stream of hydrocarbon and catalyst .is withdrawn by line 2e from reaction zone l6 and is cooled in cooler .39 containing a cooler coil 3!. The cooled stream then discharges .by line 32 into anacid separation zone 33 which, likeseparator 24, is of sufficient capacity to allow a residence time .for formation of an acid phase and any- .drocarbon phase. The acid phase inseparator 33 is generally indicated as a shaded portion at.

The acid phase may be recycled to reaction zone -I6 by line 35, pump 3t and line 58 as has been "described. Acid separator 33 is provided with a discharge line 31 controlled by valve 38 ,for withdrawal of used acid-from timeto time such as to prevent contamination thereof with car- When used acid is with- This hydrocarbon phase may be combined with the hydrocarbon phase withdrawn from separator 2a by line 21; therefore, line 21 ties into .line 4|. Valve 42 may be a pressure responsive valve and may be of the pneumatic type and suitably may be automatically controlled by connecta ing. same throughcontrol means as and :14 to reaction zone .16. Alternatively, the valve 42 may be controlled by having a suitable connection to separator 33 as shown.

.In the operation of the present invention a propylene-containing feed, for example, would beintroduced into line H and charged through analyzer l4 and line 15 into reaction zone l5 where it will .be contacted with phosphoric acid introduced by line .IB, conditions being maintained in reaction zone [6 to cause polymerization of the propylene. .In the bottomof reaction zone 18 a vaporous stream would be withdrawn by line it] and a second stream by line '29. The vaporousstream would beso proportioned sothat theamount of .water withdrawn thereby, .due to its partial pressure under ,the conditions .maintained in reactionzone 16, would be-sufficient to .maintain the acid strength at the desired v'level,

accounting, or course, for the amount of water which would be containedin the hydrocarbon stream discharged by line 4].. By continuously withdrawing a vapor stream, condensing .same and discarding water, .it is possible to control within very narrowlimits the hydration of the catalyst and thus allow. control oitho system.

By virtue of a control system including analyzer l4, valve.28 and valve .42,.it.is possible to operatethe process, described with respect to the drawing, in an automatic manner. .Assuming a wet olefinic feed ischarged toanalyzer 14, the, analyzer will transmit a signal'through the connection means 29 to valve'28 which will automatically open valve 28, to proportion properly the stream flowingthrough line .IB withrespect to'the stream flowing through line 4| to allow withdrawal of the required amount of vaporous stream containing hydrocarbon and water. The valve 42 is a back .pressure regulator and may operate from the reaction zone I6 or from the acid separator 33 .in a well known manner to control flow through line 41. If the water content of the incoming feed is such as to require release of increased amounts of vaporous hydrocarbon stream flowing through line 19, the signal to valve 28 would cause it to be opened and to change the relative proportion of the streams in line It and line 4|. Similarly, if the water content of the feed should decrease, valve 28 would bepartially closed to change the proportions of the two streams to release less .ofzthe stream in line H9 in proportion to, the stream in line 4|.

Although not shown in the drawing, the hydro carbon streams leaving the system by. lines :2! and 4| may be separately contacted with a suit-- able material such as activated alumina, silica gel, bauxite or clay to remove any phosphoric acid which may be entrained therein and toprevent corrosion of subsequentfractionating equipment.

The invention will be illustrated by -the following examples:

. Example I Anoperationis conducted with a hydrocarbon feed consisting of 60 mole per cent of propylene and 40 mole per cent of propane. The reaction temperature is 360 F., the reaction pressure is 500 p. s. i. g. and the recycled acid is 100% HsPOi. In this operation 20 parts of feed containing 250 parts per million of water is introduced into the system and it is desired to maintain the acid at 100% H3PO4. Under these conditions the vapor phase streamwithdrawnby line H) is withdrawn in an amount of 7.6 parts while the hydrocarbon stream withdrawn by line 20 is 12.4 parts. The amount of water in the stream withdrawn by line I 9 is 4.38 parts, which is the amount introduced with the feed, minus that contained in the stream withdrawn by line 4! the stream withdrawn by line 4| contains 50 parts per million of water. The strength of the acid recycled by lines 35 and I8 is substantially 100% HsPOr.

Exam ple II if it is desired to maintain the acid strength at i 100% 3PO4 with a feed having this water content, 4.45 parts of the stream withdrawn by line L! are discharged and 15.55 parts of the hydrocarbon stream withdrawn by line are discharged. The vaporous stream discharged by 1 line [9 contains 1.22 10- parts or water while the stream withdrawn by line 4| contains 50 parts per million of water. The acid phase recycled by lines and 18 has a strength substantially 100% 1131904.

The present invention has been described and illustrated with respect to a polymerization operation in which a mono-olefin is polymerized to form a polymer. It is understood that the invention is not to be limited to that particular catalytic conversion operation. The invention may be employed in other catalytic operations such as alkylation reactions where phosphoric acid catalysts of the type illustrated are employed. The invention may be practiced in any system where liquid phosphoric acid is used and water of hydration is lost by virtue of the high temperatures of a particular reaction and where a vapor phase is present in the reaction zone.

Illustrative of such operations in which liquid phosphoric acid is contacted with hydrocarbons or their derivatives at an elevated temperature include the alkylation of aromatics or of phenols With olefins.

While the invention is particularly adapted to the control of a particular acid strength, it is apparent that by virtue of the present invention in which a vapor stream is withdrawn in which the water is concentrated it is possible to either hydrate or dehydrate the catalyst. In short, it may be desirable to start an operation with a catalyst having a low acidity within the range given and then gradually increase the acid strength by increasing the amount of water withdrawn. However, on other conditions it may be desirable to begin with a strong acid and gradually hydrate the acid to lower the acid strength. It will be apparent that the present invention allows such operations to be carried out easily merely by properly proportioning the amount of the vaporous stream to be discharged.

It is understood, of course, that the amount of vaporous stream containing hydrocarbons and water withdrawn in accordance with the present invention will depend on the operating condiand to secure by Letters Patent is:

1. In a catalyticconversion process in which a wet olefinic hydrocarbon feed in vaporous condition is contacted in a reaction zone with a liquid phosphoric acid catalyst having a strength no less than 75% I-I3PO4 to form a polymer, the method of maintaining the acid strength of the catalyst which comprises contacting the said hydrocarbon feed and the acid catalyst under conditions including a temperature at least 280 F. to form a product including vaporous hydrocarbon product, water and catalyst, withdrawing from a; lower point in said zone a first stream of vaporous hydrocarbon containing water and withdrawing from a point substantially below the point where the first stream is withdrawn a second stream of hydrocarbon and acid catalyst, said first stream and said second stream being proportioned with respect to an amount or water introduced with the feed to control the strength of the acid Within the range given, separately cooling the first and second streams to a temperature no greater than 200 F., separating the cooled first stream into a first hydrocarbon phase and a water phase, discarding the water phase, separating the cooled second stream into a second hydrocarbon phase and an acid phase, and recovering and recycling to said contacting step said acid phase having a strength substantially the same as the acid catalyst,- the first stream or vaporous hydrocarbon containing water being withdrawn in an amount sufiicient to maintain the acid strength of the catalyst.

2. In a catalytic polymerization process in which a wet olefinic feed in vaporous condition is contacted in a reaction zone with a liquid phosphoric acid catalyst having a strength in the range from about 75% to 115% HZSPO4 to form a polymer, the method of maintaining the acid strength of the catalyst which comprises contacting the olefinic feed and the acid catalyst under conditions including a temperature in the range from 280 to 450 F. to form a product including vaporous hydrocarbon product, water and catalyst, withdrawing from a lower point in said zone a first stream of vaporous hydrocarbon containing water and withdrawing from a point substantially below the point where the first stream is withdrawn a second stream of hydrocarbon and acid catalyst, said first stream and said second stream being proportioned with respect to an amount of water introduced with the feed to control the strength of the acid within the range given, separately cooling the first and second streams to a temperature in the range from to 200 F., separating the cooled first stream into a first hydrocarbon phase and a water phase, discarding the water phase, separating the cooled second stream into a second hydrocarbon phase and an acid phase and recovering and recycling to said contacting step said acid phase having a strength substantially the same as the acid catalyst.

3. A method for forming a polymer which comprises polymerizing a vaporized mono-olefin having from:- 3 to 6 carbon atoms; in the. molecule containing water-by contacting same. in areaction' zone with a liquidphosphoric acidcatalyst having a strength-in therange from 75% to- 115 HaPOr at a temperature from 280 to-400 F. and ata pressure of from 3001101000 p; s...i.-g=..to-fo1'm a polymerized product including. vaporous hydrocarbon product, water and catalyst, withdrawing from a lower point in said zone: a. first stream of vaporous hydrocarbon containing water and withdrawing from. apoint. substam tiall-y below the point where the first stream is withdrawn a second stream of hydrocarbon and acid catalyst, said first stream and said second stream being proportioned with respect to an amount of water introduced with the: feed to control the strength of theacid-within therange given,v separately cooling the first and second streams; toa temperature in the range between 80 and 200 FL, separatingthe cooled first stream into a first hydrocarbon phase and a water phase, discarding the water phase, separatingthe cooled second stream into a second hydrocarbon. phase and an acid phase and recovering and recycling iii which the; mono-olefin is propylene;

5.. A. method in accordance with claim 3 in which the mono-olefin isbutylene.

6. A method in accordance with claim 3- in which themonO-olefin is amixture. of. propylene and butylene.

References Cited in the file of thi patent UNITED STATES PATENTS Number Name 7 Date.

2,136,785 Davis Nov. 15, 1938 2378;439 Schlesman June 19, 1945 2,429,622 Hirsch Oct. 28, 1947 2,436,571 Heinrich Feb. 24, 1948 2,592,428

Kemp'et a1 A-pr. 8,. 19.52 V 

1. IN A CATALYTIC CONVERSION PROCESS IN WHICH A WET OLEFINIC HYDROCARBON FEED IN VAPOROUS CONDITION IS CONTACTED IN A REACTION ZONE WITH A LIQUID PHOSPHORIC ACID CATALYST HAVING A STRENGTH NO LESS THAN 75% H3PO4 TO FORM A POLYMER, THE METHOD OF MAINTAINING THE ACID STRENGTH OF THE CATALYST WHICH COMPRISES CONTACTING THE SAID 